Method and composition for the sizing of paper using azetidinium and/or guanidine polymers

ABSTRACT

Compositions and methods are provided for the sizing of paper, to enhance the quality of images printed thereon. The novel sizing compositions contain as a sizing agent: (a) an azetidinium polymer, (b) a guanidine polymer, (c) a mixture of an azetidinium polymer and a guanidine polymer, or (d) a copolymer of an azetidinium monomer and a guanidine monomer. When applied to a paper substrate, such as in an internal or external sizing process, the sizing compositions result in a sized paper substrate that provides high quality printed images when printed with an ink containing a reactive dye having ionizable and/or nucleophilic groups capable of reacting with the sizing agent. Images printed on a paper substrate coated with the sizing compositions of the invention are bleed-resistant, water-resistant (e.g., water-fast), and/or are characterized by an enhanced chroma and hue.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a of U.S. patent application Ser. No. 09/282,595, filed Mar. 31, 1999, which is a continuation-in-part of U.S. provisional patent application 60/082,697, filed Apr. 22, 1998, both of which are incorporated herein by reference.

TECHNICAL FIELD

[0002] The present invention relates generally to the production of sized paper, and more particularly relates to a novel sizing process and novel compositions useful in conjunction therewith.

BACKGROUND

[0003] As printing technology advances, paper manufacturers are faced with the increasingly rigorous demands of their customers for high quality paper that is economically attractive. For example, there is a keen demand for papers that meet high quality standards with respect to brightness, opacity, and dry and/or wet strength, and that, upon printing with any of a wide range of colorants, provide a water-resistant printed image. The customer further demands that such papers be amenable to use with a variety of printing techniques, including not only conventional printing techniques, but also “impact free” printing techniques, e.g., inkjet printing (particularly colored inkjet printing), laser printing, photocopying, etc.

[0004] In response, paper manufacturers have attempted to meet their customers' demands for such high quality paper through a process termed “sizing.” “Sizing,” which encompasses both “internal sizing” and “external sizing,” affects the manner in which colorants and particularly ink interact with the fibers of the paper. “Internal sizing” involves introduction of sizing compositions within the entire fibrous mass at the pulp stage of paper manufacturing (i.e., to the wet pulp, or more specifically, to the prepared papermaking furnish) before the stock is formed into a sheet, resulting in the distribution of the sizing composition within the entire fibrous mass that is subsequently used to produce the flat fibrous paper sheet. “External sizing” (also termed surface application, pasting, saturating or coating) involves application of a sizing composition to at least one surface of a flat fibrous paper sheet, so that the sizing composition is present on or in at least one of the two faces of the flat fibrous sheet. Paper and paper-based products are internally and/or externally sized to increase the resulting paper's strength, resistance to picking and scuffing, and resistance to undue penetration of water, organic solvents, oils, inks, and various types of aqueous solutions. Sizing is also used to improve the paper's smoothness and optical characteristics. In general, sizing is recognized to confer a number of advantages, including but not limited to the foregoing, with perhaps resistance to penetration of water and aqueous inks (e.g., bleed resistance) of utmost importance.

[0005] Various materials have been used as external and/or internal sizing agents, such as conventional and modified starches, polyvinyl alcohol, cellulosic derivatives, gelatin, rosin, proteins such as casein, natural gums and synthetic polymers. Internal sizing agents are generally referred to as acid, neutral, or alkaline internal sizes. Acid sizes are typically rosin based and precipitated by alum. Neutral sizes may also be rosin based, and are used at near-neutral pH, while alkaline sizes are synthetic materials such as alkenyl succinic anhydride (ASA) and alkyl ketene dimer (AKD). Although these materials are effective to various degrees under certain conditions, use of each is associated with certain limitations. For example, it is often necessary to use large amounts of these conventional sizing agents in order to provide paper having the desired properties. However, the opacity and brightness of the paper substrate decreases in direct proportion to the amount of sizing agent applied to the paper. Moreover, as the amount of sizing agent and/or the cost of the sizing agent increases, the cost of producing the paper increases, making high quality papers having the desired characteristics prohibitively expensive and not economically viable. Certain sizing agents impart relatively poor bleed resistance and water resistance of imprinted inks, and thus must be used with insolubilizing agents to ensure production of a paper having satisfactory water resistance.

[0006] Conventional and modified starches are the most common sizing agents in use in the industry. Exemplary starch-based sizing agents include hydrophobic starches (see, e.g., U.S. Pat. No. 2,661,349), blends of hydrophobic and non-hydrophobic starches (see, e.g., U.S. Pat. No. 4,239,592; EP 350,668), and blends of treated starches and/or cationic starches (see, e.g., U.S. Pat. No. 4,872,951; EP 620,315; U.S. Pat. No. 5,647,898). However, while starches may provide improved porosity, these compounds generally do not provide for improved bleed resistance or water resistance of inks printed on the treated paper substrates.

[0007] Several synthetic sizing agents are presently available, and may be used in internal sizing and/or external sizing processes. Exemplary synthetic sizing agents include hydrophobic cellulose reactive sizing agents (see, e.g., U.S. Pat. Nos. 4,478,682; 3,840,486), cationic polymers (see, e.g., U.S. Pat. No. 3,006,806), and water-soluble, poly(aminoamide) resins (see, e.g., U.S. Pat. No. 4,478,682). Synthetic compounds have also been used to enhance the dry and/or wet strength of paper (see, e.g., U.S. Pat. Nos. 5,138,669; 3,058,873; 5,510,004; 5,659,011), either at the internal sizing or external sizing steps. However, synthetic sizing agents tend to be expensive, due to both the cost of the starting material and the amount that is required to provide a paper substrate having the desired characteristics.

[0008] Unfortunately, the use of sizing agents normally results in a decrease in the porosity of the final paper substrate. Thus, while the final sized paper substrate may have the desired brightness and opacity, it may not provide for a printed image that is of a desired optical density or color intensity. In addition, as the porosity of the paper increases, the paper becomes less amenable to various handling processes during manufacturing. For example, envelope manufacturers demand that the paper available to them have a relatively low porosity. If the porosity of the paper is too high, the paper is too stiff for handling by the automatic industrial devices for folding and sorting (e.g., devices of the “suction extractor” type) during envelope production. Moreover, in contrast to lower porosity papers, high porosity papers require slower machine speeds and refining and draining operations that have relatively high energy costs, both of which add up to decreases in plant productivity, efficiency, and cost effectiveness.

[0009] There is a need in the field for sizing agents and methods that provide an effective, cost efficient means for sizing paper, are amenable for use with a wide variety of paper manufacture and post-manufacture handling processes, and provide high quality, water-resistant images.

SUMMARY OF THE INVENTION

[0010] The present invention features novel sizing methods and sizing compositions, wherein the sizing compositions are composed of a sizing agent selected from one of (a) an azetidinium polymer, (b) a guanidine polymer, (c) a mixture of an azetidinium polymer and a guanidine polymer, and (d) a copolymer of an azetidinium monomer and a guanidine monomer. When applied to a paper substrate, such as in an external sizing process, the sizing compositions provide a coated paper substrate that yields high quality printed images when printed with an ink containing a reactive dye having ionizable and/or nucleophilic groups capable of reacting with the sizing agent. Images printed on a paper substrate coated with the sizing composition of the invention are bleed-resistant, water-resistant (e.g., water-fast), and/or are characterized by an enhanced chroma and hue.

[0011] It is a primary object of the invention to address the above-mentioned need in the art by providing a sizing composition that efficiently binds colorant upon printing, and thus provides an economical, efficient means for processing of paper that provides a high quality printed image.

[0012] Another object of the invention is to provide a printed, sized paper substrate that is of high quality, bleed-resistant, and provides water-resistant (e.g., water-fast) images that are of a highly desirable optical density and brightness.

[0013] Still another object of the invention is to provide a method for sizing paper using the sizing compositions of the invention.

[0014] Still an additional object of the invention is to provide a method for printing on a sized paper substrate to provide water-resistant (e.g., water-fast) images thereon.

[0015] Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by practice of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0016] Definitions and Nomenclature:

[0017] It must be noted that, as used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a sizing agent” in a composition means that more than one sizing agent can be present in the composition, reference to “a polymer,” as in “a guanidine polymer” or “an azetidinium polymer” includes more than one such polymer, and the like.

[0018] The term “paper” or “paper substrate” is meant to encompass a substrate based on cellulosic fibers; synthetic fibers such as polyamides, polyesters, polyethylene, and polyacrylic fibers; inorganic fibers such as asbestos, ceramic, and glass fibers; and any combination of cellulosic, synthetic, and inorganic fibers. The paper substrate may be of any dimension (e.g., size or thickness) or form (e.g., pulp, wet paper, dry paper, etc.). In most instances, the “paper” or “paper substrate” has not been subjected to an external sizing process prior to treatment according to the methods of the invention. Where the paper substrate is used in external sizing, the paper substrate is preferably in the form of a flat or sheet structure, which structure may be of variable dimensions (e.g., size and thickness). “Paper,” particularly as used in the context external sizing, is thus meant to encompass printing paper (e.g., inkjet printing paper, etc.), writing paper, drawing paper, and the like, as well as board materials such as cardboard, poster board, Bristol board, and the like.

[0019] The term “sheet” or “flat structure” is not meant to be limiting as to dimension, roughness, or configuration of the substrate useful with the present invention, but rather is meant to refer to a product suitable for external sizing.

[0020] “Sized paper substrate” is a paper substrate as described above that has applied to its surface and/or is saturated with one or more of the sizing compositions of the present invention. The sizing composition of the invention is preferably applied in an external sizing step, but may also be applied as a pretreatment (e.g., prior to printing), simultaneously with printing, or as an after-treatment. The sizing compositions of the invention are applied in quantities suitable to accomplish external sizing and to provide desired characteristics, such as bleed resistance, water resistance (e.g., water-fastness) of an ink printed on sized paper substrate, etc. Typical amounts of sizing composition applied generally range from about ten to about five hundred pounds per ton of paper substrate, preferably from about thirty to about five hundred pounds per ton of paper substrate.

[0021] “Aqueous based ink” refers to an ink composed of an aqueous carrier medium and a colorant, such as a dye or a pigment dispersion. An aqueous carrier medium is composed of water or a mixture of water and one or more water-soluble organic solvents. Exemplary aqueous based ink compositions are described in detail below.

[0022] “Colorant” as used herein is meant to encompass dyes, pigments, stains, and the like compatible for use with the polymer coatings of the invention.

[0023] The term “colorant-reactive component” as used herein refers to a component (e.g., a chemical moiety) of a sizing agent that is capable of reacting with a selected colorant, particularly a colorant having a nucleophilic and/or ionizable group, to form a sizing agent-colorant complex. The sizing agent-colorant complex is formed through either a covalent, electrostatic, or ionic association between the colorant-reactive component of the sizing agent and the colorant. When a sizing agent having a colorant-reactive component and a selected colorant from a sizing agent-colorant complex in the context of a printed image on a sized paper substrate, the association between the colorant and the color-reactive component of the sizing agent is effective to impart advantageous qualities to the printed image on the sized paper substrate, particularly with respect to water resistance, enhanced optical density, enhanced brightness, and the like.

[0024] The term “organic solvent” is used herein in its conventional sense to refer to a liquid organic compound, typically a monomeric organic material in the form of a liquid, preferably a relatively nonviscous liquid, the molecular structure of which contains hydrogen atoms, carbon atoms, and optionally other atoms as well, and which is capable of dissolving solids, gases or liquids.

[0025] The term “significant,” as when used with reference to “significantly enhanced brightness” or “significantly improved water-fastness” generally refers to a difference in a quantifiable, measurable, or otherwise detectable parameter, e.g., optical density, LAB graphs (color sphere), dot spread, bleed through, between the two groups being compared (e.g., unsized versus sized paper substrates) that is statistically significant using standard statistical tests. For example, the degree of visual wicking or water-fastness in a sized paper substrate as detected in a print assay may be quantified using standard methods, and the degree of wicking or water-fastness under different conditions can be compared for both sized and unsized paper substrates to detect statistically significant differences.

[0026] The term “fluid resistance” is used herein to describe the resistance of a paper substrate to penetration by a fluid, with the term “water resistance” specifically referring to resistance of a paper substrate to penetration by a fluid.

[0027] The term “water-fast,” is used herein to describe a form of water resistance, and which is normally used to refer to the nature of the ink composition after drying on a substrate. In general, “water-fast” means that the dried composition is substantially insoluble in water, such that upon contact with water, the dried ink retains at least about 70%, preferably at least about 85%, and more preferably at least about 95%, of optical density.

[0028] The term “bleed resistance” is meant to refer to the retardation of the penetration of water into paper, which retardation is associated with creation of a low energy hydrophobic surface at the fiber-water interface which increases the contact angle formed between a drop of liquid and the surface, and thus decreases the wettability. Contact angles have been shown to be sensitive to molecular packing, surface morphology, and chemical constitution of the paper substrate and any components added thereto.

[0029] The term “rub resistance” is normally meant to refer to a characteristic of the ink composition after drying on a substrate, more specifically, the ability of a printed image to remain associated with the substrate upon which it is printed despite application of force (e.g., rubbing) to the printed image. In general, “rub resistant” means that the dried ink composition is substantially resistant to rubbing force so that the dried ink retains at least about 70%, preferably at least about 85%, and more preferably at least about 95%, of optical density after rubbing of the printed image.

[0030] The term “alkyl” as used herein refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.

[0031] The term “alkylene” as used herein refers to a difunctional, branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, including without limitation methylene, ethylene, ethane-1,1-diyl, propane-2,2-diyl, propane-1,3-diyl, butane-1,3-diyl, and the like. “Lower alkylene” refers to an alkylene group of 1 to 6 carbon atoms.

[0032] The term “alkoxy” as used herein intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be defined as —OR where R is alkyl as defined above. A “lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.

[0033] “Halo” or “halogen” refers to fluoro, chloro, bromo or iodo, and usually relates to halo substitution for a hydrogen atom in an organic compound.

[0034] The term “polymer” is used herein in its conventional sense to refer to a compound having two or more monomer units, and is intended to include homopolymers as well as copolymers. The term “monomer” is used herein to refer to compounds that are not polymeric.

[0035] “Optionally” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” aromatic ring means that the aromatic ring may or may not be substituted and that the description includes both an unsubstituted aromatic ring and an aromatic ring bearing one or more substituents.

[0036] Overview of the Invention:

[0037] The present invention is based upon the discovery that a composition having a sizing agent that is one of (a) an azetidinium polymer, (b) a guanidine polymer, (c) a mixture of an azetidinium polymer and a guanidine polymer, or (d) a copolymer of an azetidinium monomer and a guanidine monomer, is highly effective as a sizing composition. Paper that has been treated with a sizing composition of the invention ultimately provides high quality printed images having improved color fastness (printed images which do not run when exposed to moisture) and exhibits substantially non-reversible binding of aqueous colorants. These images are therefore characterized as “water-resistant” or “water-fast” due to the characteristics of the printed image following exposure to water.

[0038] The sized paper substrates of the invention can be used in conventional printing, or with digital printing (particularly inkjet printing, including drop-on-demand and continuous printing) to provide highly brilliant, printed images that are significantly improved in color quality, for example, with respect to chroma and hue, when compared to unsized paper substrates and/or to paper substrates sized with conventional sizing compositions. The sizing compositions and their methods of use according to the present invention thus provide a number of advantages over conventional sizing methods and sizing compositions.

[0039] The sizing compositions, methods of sizing using the sizing compositions described herein, and other features of the invention are described in greater detail below.

[0040] Sizing Compositions:

[0041] The sizing compositions of the invention are composed of a sizing agent selected from the group consisting of (a) an azetidinium polymer, (b) a guanidine polymer, (c) a mixture of an azetidinium polymer and a guanidine polymer, and (d) a copolymer of an azetidinium monomer and a guanidine monomer. In general, the sizing agents have a colorant-reactive component, which is capable of reacting with a selected colorant, particularly a colorant having a nucleophilic and/or ionizable group, to form a sizing agent-colorant complex through a covalent, electrostatic, or ionic association. The association of the sizing agent and colorant imparts bleed resistance, water resistance (e.g., water-fastness), and other desirable characteristics to the printed sized paper substrate. In addition to the sizing agent, the sizing compositions can include components such as binders, pigments, and other additives.

[0042] The present sizing compositions can be readily prepared from commercially available starting materials and/or reagents, are compatible with additional binders or additives, can be used with a variety of base papers, and are compatible with a variety of printing methods, including conventional and digital printing methods (particularly inkjet printing, including drop-on-demand printing and continuous printing), and can also be used with existing commercial paper production processes and equipment. The sizing composition is inexpensive to prepare, and due to their efficacy, generally less sizing agent is needed to provide a sized paper substrate having the advantageous features described herein. The sizing compositions of the invention are also easy to handle due to their solubility in water (i.e., the sizing agents are hydrophilic polymers), and do not require the use of large volumes of organic solvents. The novel sizing compositions herein also possess good film-forming properties.

[0043] The sized paper substrate prepared using the composition of the invention exhibits improved durability, as evidenced by improved paper strength (e.g., tear strength), and stability upon prolonged storage. The sized paper does not discolor or yellow, and maintains a high degree of brightness for extended periods of time. Paper substrates treated with the sizing compositions of the invention react rapidly and substantially irreversibly with a number of aqueous based colorants, thus providing a versatile sizing system for use with a wide variety of available colorants. Furthermore, because the colorant reacts quickly with the sizing compositions, the sized printed substrate does not require a separate curing step, but rather is fast-drying. This fast-drying characteristic provides for printed images that are “non-sticky,” thus allowing the printed sized paper substrate to be handled immediately after printing, for example, to allowing stacking. The sized paper substrate of the invention can also be used to prepare images with varying degrees of gloss, depending upon variations in pigment.

[0044] In addition to their water resistance, paper substrates sized with a sizing composition of the invention are highly bleed-resistant (as evidenced by small dot size measurements, i.e., less wicking action) and rub-resistant.

[0045] The various components of the sizing compositions will now be described.

[0046] Sizing Agents

[0047] Sizing agents in the sizing compositions of the invention generally comprise an azetidinium polymer, a guanidine polymer, a copolymer of an azetidinium monomer and a guanidine monomer, or a mixture of an azetidinium polymer and a guanidine polymer. In general, the sizing agent represents approximately 5 wt. % to 95 wt. % of the sizing composition, typically 10 wt. % to 95 wt. % of the sizing composition, based upon total solids weight of the composition after drying.

[0048] Azetidinium Polymers

[0049] In one embodiment, the sizing agent is an azetidinium polymer. An “azetidinium polymer” is a polymer comprised of monomeric subunits containing a substituted or unsubstituted azetedine ring (i.e., a four membered nitrogen-containing heterocycle). In general, the azetidinium polymers useful herein are composed of monomer units having the structural formula (I):

[0050] in which R¹ and R² are independently lower alkylene, X⁻ is an anionic, organic or inorganic counterion, and Y¹, Y² and Y³ are selected from the group consisting of hydrogen, hydroxyl, halo, alkoxy, alkyl, amino, carboxy, acetoxy, cyano and sulfhydryl. Preferred such polymers are wherein R¹ and R² are methylene, X⁻ is selected from the group consisting of halide, acetate, methane sulfonate, succinate, citrate, malonate, fumarate, oxalate and hydrogen sulfate, Y¹ and Y³ are independently hydrogen or lower alkyl, and Y² is hydrogen or hydroxyl. In particularly preferred azetidinium polymers herein, Y¹ and Y³ are hydrogen and Y² is hydroxyl.

[0051] The azetidinium polymer may be a homopolymer, or it may be a copolymer, wherein one or more non-azetidinium monomer units are incorporated into the polymer structure. Any number of comonomers may be employed to form suitable azetidinium copolymers for use herein; however, a particularly preferred azetidinium copolymer is aminoamide azetidinium. Further, the azetidinium polymer may be essentially straight-chain or it may be branched or crosslinked.

[0052] Azetidinium polymers can associate with colorant in two different ways. First, the azetidinium polymer can associate with colorant through an ionic interaction, where the colorant provides anionic groups, such as carboxy or sulfonate, that can ion-exchange with the polymer counterions (X⁻ in Formula (I), above), thus fixing the colorant to the sized paper substrate via an electrostatic-type interaction. Second, nucleophilic groups present within the colorant can react with the azetidinium groups of the polymer via a ring-opening reaction. A characteristic ring-opening reaction of an azetidinium polymer of the invention may be illustrated as follows:

[0053] The colorant (“-Nuc⁻) thus covalently bonds to the polymer coating, to form a cross-linked polymer-colorant complex. Colorant thus applied to a sized substrate is rapidly and irreversibly bound to the paper substrate.

[0054] The percentage of reactive azetidinium groups in the polymer can be adjusted in a controlled manner to tailor the number of reactive groups in the polymer. Azetidinium groups are insensitive to pH change; however, such groups are highly sensitive to the presence of anionic and nucleophilic species. In some cases, it may be desirable to adjust the reaction conditions used to prepare the azetidinium polymer (e.g., by raising the pH) to generate anionic groups within the polymer, which then participate in intramolecular crosslinking.

[0055] A preferred azetidinium polymer for use in the present invention is shown in Formula (II)

[0056] Commercially available such polymers include “AMRES®,” available from Georgia Pacific Resins, Inc., Atlanta, Ga., “KYMENE®,” from Hercules, Inc., Wilmington, Del., and “Polycup®,” also from Hercules, Inc. These azetidinium polymers are generally referred to as poly(aminoamide)-epichlorohydrin (PAE) resins; such resins are typically prepared by alkylating a water-soluble polyamide containing secondary amino groups with epichlorohydrin. Other suitable azetidinium polymers will be known to those skilled in the art and/or are described in the pertinent texts, patent documents, and literature references; see, for example, Moyer, et al., in WET STRENGTH IN PAPER AND PAPERBOARD, Tappi Monograph Series No. 29, Tappi Press, Ch. 3, p. 33-37 (1965); Chan, in TAPPI WET AND DRY STRENGTH SHORT COURSE, Tappi Press, Atlanta, Apr. 13-15, 1988; and Espy, in WET STRENGTH RESINS AND THEIR APPLICATION, Ed., Lock L. Chan, Tappi Press, Atlanta, Ga. (1994).

[0057] (B) Guanidine Polymers

[0058] In another embodiment, the sizing agent is a guanidine polymer, also termed a “polyguanidine.” The guanidino group is extremely basic, possessing a pKa of about 12-13. Polyguanidine polymers for use in the invention are typically provided as acid salts wherein the imine nitrogen atoms are for the most part in protonated form.

[0059] In general, guanidine polymers useful as sizing agents in the present invention are either homopolymers or copolymers. All guanidine polymers herein are comprised of recurring monomer units having the structural formula

[0060] wherein R³ is hydrogen or lower alkyl and R⁴ is hydrogen, alkyl, alkoxy, or hydroxyl-substituted alkoxy. Preferably, R³ and R⁴ are hydrogen. Particularly preferred guanidine polymers for use herein are comprised of monomer units having the structural formula (IV)

[0061] wherein n is an integer in the range of 1 to 10 inclusive, R³ is hydrogen or lower alkyl and R⁴ is hydrogen, alkyl, alkoxy, or hydroxyl-substituted alkoxy. Preferably, R³ and R⁴ are hydrogen.

[0062] A particularly preferred guanidine polymer for use in the methods and compositions of the invention has the structure of formula (IV) wherein R³ and R⁴ are H and n is 6 (3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide), available under the tradenames “BAQUACIL®” and “VANTOCIL®,” from Zeneca, Inc.

[0063] Polyguanidine polymers of the invention react electrostatically with anionic groups present in the dye via ion-exchange type interactions, to rapidly and irreversibly bind anionic type dyes to print substrates coated with such polymers.

[0064] (C) Mixtures of Azetidinium Polymers and Guanidine Polymers

[0065] In another embodiment, the sizing agent comprises a mixture of an azetidinium polymer and a guanidine polymer. The two polymers may be present in any suitable ratio relative to one another. The relative amounts of polyguanidine and polyazetidinium can range from about 0.05% polyguanidine/99.95% polyazetidinium to 0.05% polyazetidinium/99.95% polyguanidine. The actual relative amounts of polyguanidine and polyazetidinium will vary according to the composition of the ink to be used (e.g., the nature of the colorant in the ink), the nature of the paper substrate, and other factors affecting the use of the polymers, such as the relative market price for each polymer. In general, it is preferable to use a smaller amount of guanidine relative to azetidinium.

[0066] In this embodiment, it is important that the pH of the sizing composition be acidic, as the composition tends to gel at basic pH. If necessary, then, an acid should be added to the sizing composition to ensure that the pH is below 7.0, preferably less than about 5.5, and most preferably in the range of about 1.0 to 5.5. Suitable acids include sulfuric acid, hydrochloric acid, acetic acid, and the like.

[0067] Although it will be appreciated that any of a number of azetidinium or guanidine polymers can be used to prepare the sized substrates and sizing compositions described herein, a preferred polymer is a poly (aminoamide)-azetidinium polymer, e.g., a polyazetidinium chloride-based polymer, such as a polyamide-polyamine-epichlorohydrin resin.

[0068] (D) Copolymers of Azetidinium Monomers and Guanidine Monomers

[0069] In another embodiment, the sizing agent is a copolymer of an azetidinium monomer unit and a guanidine monomer unit. In general, the azetidinium monomer unit has the structural formula (I)

[0070] in which R¹ and R² are independently lower alkylene, X⁻ is an anionic, organic or inorganic counterion, and Y¹, Y² and Y³ are selected from the group consisting of hydrogen, hydroxyl, halo, alkoxy, alkyl, amino, carboxy, acetoxy, cyano and sulfhydryl. Preferred monomers are wherein R¹ and R² are methylene, X⁻ is selected from the group consisting of halide, acetate, methane sulfonate, succinate, citrate, malonate, fumarate, oxalate and hydrogen sulfate, Y¹ and Y³ are independently hydrogen or lower alkyl, and Y² is hydrogen or hydroxyl. In particularly preferred azetidinium monomers, Y¹ and Y³ are hydrogen and Y² is hydroxyl. The guanidine monomer has the structural formula (III)

[0071] or the structural formula (IV)

[0072] wherein R³, R⁴ and n are as defined earlier herein.

[0073] The ratio of azetidinium monomers to guanidine monomers in the copolymer, as well as the distribution of each monomer type in the copolymer, can be varied according to a number of factors, and may be, for example, tailored for use with specific colorants having certain types of ionic and/or nucleophilic groups. The precise composition of the copolymer may also be varied to best accommodate the nature of the paper substrate to be sized.

[0074] Film-Forming Binders

[0075] The sizing compositions of the invention preferably include a film-forming binder. By “film-forming binder” is meant a substance that provides for improved strength of a paper substrate upon application of the substance to the substrate. “Film-forming binders” used in connection with the sizing compositions of the invention include any film-forming binder that is compatible with the sizing agent of the composition. Exemplary film-forming binders include, but are not necessarily limited to: polysaccharides and derivatives thereof, e.g., starches, cellulosic polymers, dextran and the like; polypeptides (e.g., collagen and gelatin); and synthetic polymers, particularly synthetic vinyl polymers such as poly(vinyl alcohol), poly(vinyl phosphate), poly(vinyl pyrrolidone), vinyl-pyrrolidone-vinyl acetate copolymers, vinyl alcohol-vinyl acetate copolymers, vinyl pyrrolidone-styrene copolymers, and poly(vinylamine), and cationic film-forming binders such as quaternized vinyl pyrrolidone-dimethylaminoethyl-methacrylate copolymer, dimethylaminoethyl-methacrylate-co-methyl methacrylate, polydiallyldimethyl ammonium chloride and quaternized aminoacrylate polymers. The sizing agents herein are themselves film-forming substances; however, it is generally desirable to use these sizing agent compositions with additional film-forming substances.

[0076] Polysaccharide binders: Starches, as noted above, represent one category of suitable film-forming binders for use herein. Suitable starches may be any of a variety of natural, converted, and synthetically modified starches. Exemplary starches include, but are not necessarily limited to starch (e.g., SLS-280 (St. Lawrence Starch)), cationic starches (e.g., Cato-72 (National Starch), hydroxyalkylstarch, wherein the alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from about 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, or the like (e.g., hydroxypropyl starch #02382 (PolySciences, Inc.), hydroxyethyl starch #06733 (PolySciences, Inc.), Penford Gum 270 and 280 (Penford), and Film-Kote (National Starch)), starch blends (see, e.g., U.S. Pat. No. 4,872,951, describing a blend of cationic starch and starch treated with an alkyl or alkenyl succinic anhydride (ASA), preferably 1-octenyl succinic anhydride (OSA)), and the like. The film-forming binder can also be a synthetically produced polysaccharide, such as a cationic polysaccharide esterified by a dicarboxylic acid anhydride (see, e.g., U.S. Pat. No. 5,647,898). Additional saccharide binders include cellulosic materials such as alkyl celluloses, aryl celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, hydroxy alkyl celluloses, dihydroxyalkyl cellulose, dihydroxyalkyl cellulose, hydroxy alkyl hydroxy alkyl cellulose, halodeoxycellulose, amino deoxycellulose, dialkylammonium halide hydroxy alkyl cellulose, hydroxyalkyl trialkyl ammonium halide hydroxyalkyl cellulose, dialkyl amino alkyl cellulose, carboxy alkyl cellulose salts, cellulose sulfate salts, carboxyalkylhydroxyalkyl cellulose and the like). Still additional film-forming binders of this type include dextran (e.g., dialkyl aminoalkyl dextran, amino dextran, and the like), carrageenan, Karaya gum, xanthan, guar and guar derivatives, (e.g., carboxyalkyl hydroxyalkyl guar, cationic guar, and the like), and gelatin.

[0077] Additional exemplary film-forming binders for use in the sizing compositions of the invention include resins (e.g., such as formaldehyde resins such as melamine-formaldehyde resin, urea-formaldehyde resin, alkylated urea-formaldehyde resin, and the like ), acrylamide-containing polymers (e.g., poly(acrylamide), copolymers, poly(N,N-dimethylacrylamide), and the like), poly(alkyleneimine)-containing polymers (e.g., poly(ethyleneimine), poly(ethyleneimine) epichlorohydrin, alkoxylated poly(ethylene imine), and the like), polyoxyalkylene polymers (e.g., poly(oxymethylene), poly(oxyethylene), ethylene oxide/propylene oxide copolymers, ethylene oxide/2-hydroxyethyl methacrylate/ethylene oxide and ethylene oxide/hydroxypropyl methacrylate/ethyleneoxide triblock copolymers, ethylene oxide-4-vinyl pyridine/ethylene oxide triblock copolymers, ethylene oxide-isoprene/ethylene oxide triblock copolymers, epichlorohydrin-ethylene oxide copolymer, and the like), etc.

[0078] Any suitable mixtures of the above exemplary film-forming binders can be used in any effective relative amounts, although typically the film-forming binder, if present, represents approximately 1 wt. % to 40 wt. %, preferably 1 wt. % to 25 wt. %, most preferably 1 wt. % to 15 wt. % of the composition, after drying on a substrate. Starches and latexes are of particular interest because of their availability and applicability to paper.

[0079] Other Sizing Composition Components

[0080] Additional sizing composition components may include, but are not necessarily limited to, inorganic fillers, anti-curl agents, or additional conventional components such as a surfactant, plasticizer, humectant, UV absorber, light fastness enhancer, polymeric dispersant, dye mordant, optical brightener, or leveling agent, as are commonly known in the art. Illustrative examples of such additives are provided in U.S. Pat. Nos. 5,279,885 and 5,537,137. The sizing compositions may additionally contain a colorant (e.g., a pigment, dye (e.g., ionizable dye, nucleophilic dye, etc.), or other colorant) to provide for whiteness or color of the sized paper substrate. The sizing compositions may also further include a crosslinking agent, such as zirconium acetate, ammonium zirconium carbonate, or the like, for intramolecular and/or intermolecular crosslinking of sizing agent(s) in the sizing composition and/or a chelating agent such as boric acid. Additional components that may be desirable for use in the sizing compositions of the invention, as well as guidance for the use of such components and a general description of paper chemistry, are found in PAPER CHEMISTRY, 2^(nd) Edition, Roberts, ed., Blackie Academic & Professional, Glasgow, UK (1994).

[0081] The sizing composition will generally be provided in an aqueous liquid vehicle, although small amounts of a water-soluble organic solvent may be present. The aqueous liquid vehicle will generally be water, although other nonorganic compounds that are either water soluble or waters miscible may be included as well. It may on occasion be necessary to add a solubilizing compound during preparation of the sizing composition so that the components dissolve in the aqueous liquid vehicle, e.g., an inorganic base such as ammonia and/or an organic amine. Suitable organic amines include lower alkyl-substituted amines such as methylamine, dimethylamine, ethylamine, and trimethylamine, as well as ethanolamine, diethanolamine, triethanolamine, and substituted ethanolamines, typically lower alkyl-substituted ethanolamines such as N-methyl and N,N-dimethyl ethanolamines, and morpholine. Such compounds are also useful for bringing the pH into the desired range for basic formulations, and, if present, will generally represent not more than about 20 wt. % of the composition, and in most cases will represent not more than about 10 wt. % of the composition.

[0082] Application of Sizing Compositions to Paper Substrates:

[0083] The sizing compositions of the invention can be applied to a substrate, e.g., a paper substrate, by any of a number of conventional processes commonly employed in the art. Generally, the sizing compositions of the invention are applied by means of a rod, roll, flexopress, blade, or air-knife coater in amounts ranging from about 10 to 500, preferably 30 to 500, pounds per ton of substrate. For external sizing, the sizing composition is applied to a paper substrate to achieve a desired sizing composition layer thickness selected according to the particular application. Application of a coating in a selected thickness can readily be done by one of skill in the art using known techniques, for example, by varying the sizing agent concentration and number of coatings and through selection of the application means.

[0084] The sizing composition as described above is applied to any desirable paper substrate, usually to a type of paper substrate commonly used in printing. Substrates for use in the invention include cellulose and non-cellulose type substrates (e.g., synthetic fibers such as polyamides, including nylon, polyesters, polyethylene, and polyacrylic fibers; protein-based fibers such as silk; inorganic fibers such as asbestos, ceramic, and glass fibers), and/or any combination of cellulosic, synthetic, and inorganic fibers, with porous cellulose substrates being preferred. Preferred substrate for use herein is generally free cut sheet paper, with exemplary paper substrates including, but not limited to, copier grade paper, business card stock, resin-coated papers, cartons such as milk cartons and cardboard gift boxes. Additional exemplary substrates for use in the invention include polyester films such as “MYLAR” flexible film, polysulfones, cellulose triacetates, and the like. Coated transparent films are also contemplated.

[0085] Sizing Processes:

[0086] In general, sizing encompasses both internal and external sizing. “Internal sizing” generally involves introduction of sizing compositions at the pulp stage of paper manufacturing, resulting in the distribution of the sizing composition within the fibrous mass subsequently used to produce a flat fibrous structure, e.g., a sheet of paper. “External sizing,” also called surface application, pasting, saturating, or coating, involves application of a sizing composition to at least one surface of a flat fibrous paper structure, so that the sizing composition is present on or in at least one of the two faces of the flat fibrous paper. External sizing also saturates the paper to various extents depending on the degree of internal sizing.

[0087] Internal sizing processes are well known in the art. Generally, internal sizing is accomplished by adding the sizing agent to the pulp, preferably with continuous mixing at the dosing point. In general, the external sizing process of the invention involves application of a sizing composition of the invention to a surface of a paper substrate. Any suitable technique can be used for application of the sizing compositions of the invention as an internal or external sizing agent for a paper substrate. Exemplary external sizing techniques include, but are not necessarily limited, to, size press treatment, dip coating, reverse roll coating, extrusion coating, and the like. For example, the sizing composition can be applied with a size press by dip coating and can be applied by solvent extrusion. The size press can be a sheet-fed size press or a size press employing a continuous web, preferably a continuous web size press.

[0088] The invention also features a paper substrate that has been sized using the sizing compositions and methods of the invention as described above. As noted in the preceding section, the sized paper substrate may be cellulosic or non-cellulosic, and may comprise any combination of cellulosic, synthetic and inorganic fibers. The sized paper substrate may be of any size and is preferably in the form of a flat or sheet structure, which may be of variable dimensions. Of particular interest in the present invention are sized paper substrates that are suitable for use in as inkjet printing paper, writing paper, drawing paper, and the like.

[0089] Method for Providing Water-Resistant Images on Paper:

[0090] The invention also features a method for providing a water-resistant (e.g., water-fast) image on paper by first applying to the surface of a paper substrate a sizing composition of the invention to the surface of a paper substrate to produce a sized substrate, and then applying a colorant to the sized substrate, where the colorant contains reactive ionizable and/or nucleophilic groups capable of reacting with the sizing agent.

[0091] In general, aqueous inks are used in the preparation of a printed image on the sized paper substrates of the invention. The aqueous ink may be any suitable ink having a colorant, e.g., a pigment, dye, or stain, having one or more reactive groups suitable for reacting, either covalently or ionically, with a colorant-reactive component of a sizing agent of the sizing composition present on the sized paper substrate. The selection of the specific ink and the colorant of the ink can vary with colorant-reactive component of the sizing agent used in the sizing composition. For example, where the colorant-reactive component is an azetidinium group, the colorant has a nucleophilic group for reaction with the azetidinium group. Thus, preferred colorants for use in printing on a sized paper substrate having a polyazetidinium polymer in the polymer coating are those containing one or more nucleophiles, e.g., having an amino, carboxy, sulfonato, thiosulfonato, cyano, hydroxy or sulfido group or the like. Preferred colorants for use in printing a sized paper substrate having a polyguanidine polymer in the polymer coating are those containing an anionic group, e.g., having a carboxy, sulfonato, thiosulfonato, cyano, halo, or phosphonato group or the like.

[0092] Preferably, the inks used in conjunction with the sized paper substrate of the invention are inkjet inks. Water-soluble colorants for use in the invention may be acid dyes, direct dyes, basic dyes or dispersive dyes, and preferred dyes for use in the invention are described in U.S. Pat. Nos. 5,425,805, 5,537,137, and 5,441,561.

[0093] The selection of the aqueous based ink will depend upon the requirements of the specific application, such as desired surface tension, viscosity, drying time, the type of paper substrate upon which the ink is to be applied (printing medium), and the like. The aqueous liquid vehicle of inks suitable for use in the invention will generally be deionized water, although other nonorganic compounds which are either water soluble or water miscible may be included as well. The colorant may be dissolved, dispersed or suspended in the aqueous liquid vehicle, and is present in an amount effective to provide the dried ink with the desired color and color intensity.

[0094] In some instances, the dye is contained in a carrier medium composed of ink and a water soluble organic solvent. For applications utilizing such a carrier medium, representative solvents include polyols such as polyethylene alcohol, diethylene glycol, propylene glycol, and the like. Additional solvents are simple alcohols such as ethanol, isopropanol and benzyl alcohol, and glycol ethers, e.g., ethylene glycol monomethyl ether, diethylene glycol monoethyl ether. Representative examples of water soluble organic solvents are described in U.S. Pat. No. 5,085,698 and U.S. Pat. No. 5,441,561.

[0095] Preferred colorants contained in the inks useful with the invention are dyes, including azo or “direct” dyes as well as dyes containing acidic groups (e.g., carboxylate, phosphonate or sulfonate moieties), basic groups (e.g., unsubstituted amines or amines substituted with 1 or 2 alkyl, typically lower alkyl, groups), or both. Specific examples of suitable colorants include, but are not limited to, the following: Dispersol Blue Grains (Zeneca, Inc.), Duasyn Acid Blue (Hoechst Celanese), Duasyn Direct Turquoise Blue (Hoechst Celanese), Phthalocyanine blue (C.I. 74160), Diane blue (C.I. 21180), Pro-jet Cyan 1 (Zeneca, Inc.), Pro-jet Fast Cyan 2 (Zeneca, Inc.), Milori blue (an inorganic pigment equivalent to ultramarine) as cyan colorants; Dispersol Red D-B Grains (Zeneca, Inc.), Brilliant carmine 6B (C.I. 15850), Pro-jet magenta 1 (Zeneca, Inc.), Pro-jet Fast magenta 2 (Zeneca, Inc.), Brilliant Red F3B-SF (Hoechst Celanese), Red 3B-SF (Hoechst Celanese), Acid Rhodamine (Hoechst Celanese), Quinacridone magenta (C.I. Pigment Red 122) and Thioindigo magenta (C.I. 73310) as magenta colorants; Dispersol Yellow D-7G 200 Grains (Zeneca, Inc.), Brilliant yellow (Hoechst Celanese), Pro-jet yellow 1 (Zeneca, Inc.), Pro-jet Fast Yellow 2 (Zeneca, Inc.), benzidine yellow (C.I. 21090 and C.I. 21100) and Hansa Yellow (C.I. 11680) as yellow colorants; organic dyes; and black materials such as carbon black, charcoal and other forms of finely divided carbon, iron oxide, zinc oxide, titanium dioxide, and the like. Specific and preferred black colorants include Acid Black 48 (Aldrich), Direct Black 58756 A (Crompton & Knowles), BPI Molecular Catalytic Gray (Brain Power), Fasday Cool Gray (Hunter Delator), Dispersol Navy XF Grains (Zeneca, Inc.), Dispersol Black CR-N Grains (Zeneca, Inc.), Dispersol Black XF Grains (Zeneca, Inc.), Disperse Black (BASF), Color Black FW 18 (Degussa), Color Black FW200 (Degussa), Hostafine Black TS (Hoechst Celanese), Hostafine Black T (Hoechst Celanese), Duasyn Direct Black (Hoechst Celanese), Pro-jet Black 1 (Zeneca, Inc.) and Pro-jet Fast Black 2 (Zeneca, Inc.).

[0096] Printed Paper:

[0097] The invention also features a printed, sized paper substrate produced using the methods and compositions described herein. The printed, sized paper substrate of the invention can be produced by any of a variety of printing techniques, including inkjet printing, laserjet printing, photocopying, and the like. In general, the printing process involves applying an aqueous recording liquid to a sized paper substrate in an imagewise pattern. Inkjet printing processes are well known in the art; see, for example, U.S. Pat. Nos. 4,601,777; 4,251,824; 4,410,899; 4,412,224; and 4,532,530.

[0098] The sized paper substrates of the invention can also be used in printing and/or copying process using dry or liquid electrophotographic-type developers, such as electrophotographic processes, ionographic process, and the like. The sized paper substrates of the invention can additionally be used in a process for generating images that involves generating an electrostatic latent image on an imaging member in an imaging apparatus, developing the latent image with a toner, transferring the developed image to a sized paper substrate of the invention. Electrophotographic processes are known in the art; see, e.g., U.S. Pat. No. 2,297,691. Ionographic and electrographic processes are also well known in the art; see, e.g., U.S. Pat. Nos. 3,611,419; 3,564,556; 4,240,084; 4,569,584; 2,919,171; 4,524,371; 4,619,515; 4,463,363; 4,254,424; 4,538,163; 4,409,604; 4,408,214; 4,365,549; 4,267,556; 4,160,257; and 4,155,093.

[0099] The sized paper substrate of the invention can also be used in any other printing or imaging processes, such as offset printing, printing with pen plotters, handwriting with ink pens, and the like.

Experimental

[0100] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to prepare and use the compounds disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in EC and pressure is at or near atmospheric.

[0101] Also, in these examples, unless otherwise stated, the abbreviations and terms employed have their generally accepted meanings. Abbreviations and tradenames are as follows (note that suppliers of each material are indicated as well):

[0102] Amres=azetidinium polymer (Georgia Pacific);

[0103] Gum 280=starch (Penford);

[0104] Polectron=styrene/poly(vinyl pyrrolidone) copolymer (Polectron 430, ISP Technologies);

[0105] PVOH=polyvinyl alcohol (Airvol 523S, Air Products);

[0106] PVP=polyvinyl pyrrolidone (Aldrich);

[0107] Sif=fumed silica (Aerosil MOX 170, Degussa);

[0108] Sip=precipitated silica (FK310, Degussa);

[0109] Tinopal=brightener (Ciba Additives);

[0110] Vantocil=3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, 20% aqueous solution (Vantocil IB, Zeneca, Inc.).

[0111] All patents, patent applications, journal articles and other references mentioned herein are incorporated by reference in their entireties.

EXAMPLE 1 Polyazetidinium-Based Size Press Coatings

[0112] The following table summarizes exemplary sizing compositions in accordance with the invention, wherein the sizing agent is an azetidinium polymer. Each of the representative formulations was effective to produce a sized substrate having the beneficial features described herein, i.e., with respect to bleeding, wicking and water-fastness. Formulation Starch Azetidinium Binder Styrene/PVP Pigment Viscosity, No. (Gum 280) (“Amres”) (PVOH) (“Polectron”) 1:4 Sif:Sip % Solids cP pH 84-1 53 20 7.0 20.0 14.5 85-1 52.5 20 7.0 20.0 14.6 74-2 22 38 8.0 32.0 13.3 74-3 22 40 10.0 28.0 13.3 335 3.82 74-4 10 50 10.0 25.0 13.3 79-1 13 50 11.0 26.0 16.3 3.75 71-2 22 36 9.4 32.8 25.3 3.74 76-1 22 38 6.0 2.0 32.0 13.3 348 3.73 76-2 22 36 6.0 4.0 32.0 13.3 74-1 22 33 8.0 5.0 32.0 13.3 479 3.86 76-3 22 34 6.0 6.0 32.0 13.3 286 3.73 77-3 22 35 5.0 6.0 32.0 13.3 77-2 22 34 5.0 7.0 32.0 13.3 250 3.73 72-2 22 33 5.0 8.0 32.0 23.1 3.74 78-2 22 33 5.0 8.0 32.0 14.1 667 4.0 77-4 22 38 10.0 10.0 20.0 13.1 3.79 79-2 35 10 10.0 10.0 35.0 18.8 4.10 77-1 27.5 47.5 12.5 12.5 10.8 3.75 78-1 22 33 5.0 8.0 32 15.4 182 6.70 90-1 23 30 10.0 35 14.5 90-2 23 30 10.0 35 14.7 90-3 23 30 10.0 35 13.4 90-4 23 30 10.0 35 14.5

EXAMPLE 2 Polyguanidine-Based Size Press Coatings

[0113] The following table summarizes exemplary sizing compositions in accordance with the invention, wherein the sizing agent is a polyguanidine, an azetidinium polymer, or wherein the sizing agent comprises a mixture of a polyguanidine and an azetidinium polymer. Each of the representative formulations was effective to produce a sized substrate having the beneficial features described herein, i.e., with respect to bleeding, wicking and water-fastness. Formulation Starch Azetidinium Polyguanidine Binder Styrene/PVP Pigment Solids No. (Gum 280) (“Amres”) (“Vantocil”) (PVOH) (“Polectron”) 1:4 Sif:Sip (%) Tinopal pH 46-2 45 17 10 28.0 14.2 79-3 45 17 10 28.0 17.6 4.71 84-3 54 10 5 8 22.5 15.2 84-2 60 10 5 5 20.0 14.8 83-3 46 15 2 7 30.0 16.4 83-2 40 20 3 7 30.0 16.5 83-1 37 25 5 5 28.0 16.4 73-1 10 50 5 10 25.0 24.0 3.94 73-2 35 5 5 10 10 35.0 18.1 4.40 88-1 50 10 5 5 30 14.5 6.61 88-2 50 10 5 5 30.0 14.5 6.62 89-3 25 10 10 5 5 40 16.2 5.0 89-2 38 12.4 4.8 9.5 4.8 28.6 14.3 1.90 88-3 55 10 5 5 23 14.0 2.0 89-1 40 13 5 10 30 13.8 2.0 51-5 60 40 12.5 52-1 50 50 13.3 55-2 71.4 14.3 6.0 55-3 85.5 17.1 5.4 51-4 25 25 50 20.0 53-4 90 10 6.0 53-1 73.7 26.3 4.8 53-2 54.5 22.7 22.7 5.5 54-4 71.4 14.3 14.3 6.6 57-1 71 14 14 6.6 

1. A paper product sized by the process comprising applying directly to an exposed surface of a paper substrate a single sizing composition comprised of (a) a sizing agent selected from the group consisting of (i) an acidic salt of a guanidine polymer comprised of monomer units having the structural formula (IV)

 wherein R³ is hydrogen or lower alkyl and R⁴ is hydrogen, alkyl, alkoxy, or hydroxyl-substituted alkoxy, (ii) a mixture of an azetidinium polymer and an acidic salt of a guanidine polymer comprised of monomer units having the structural formula (IV) as described above, and (iii) a copolymer of an azetidinium monomer and a guanidine monomer, wherein the sizing agent represents approximately 5 wt. % to 95 wt. % of the sizing composition, based upon total solids weights of the sizing composition after drying; (b) optionally, up to 40 wt. % of a film-forming binder, wherein if the sizing agent is (i), or (iii), the film-forming binder is present; and (c) a liquid vehicle, wherein the sizing agent is admixed with the liquid vehicle prior to direct application of the sizing composition to the substrate surface.
 2. The paper produce of claim 1, wherein the sizing agent comprises an acidic salt of a guanidine polymer comprised of monomer units having the structural formula (IV).
 3. The paper produce of claim 1, wherein the sizing agent comprises a mixture of an azetidinium polymer and an acidic salt of a guanidine polymer comprised of monomer units having the structural formula (IV).
 4. The paper produce of claim 1, wherein the sizing agent comprises a copolymer of an azetidinum monomer and a guanidine monomer.
 5. A printed paper product prepared by a method, comprising the steps of: (A) applying to an exposed surface of a paper substrate a sizing composition comprised of (1) a sizing agent selected from the group consisting of (a) an acidic salt of a guanidine polymer comprised of monomer units having the structural formula (IV)

 wherein R³ is hydrogen or lower alkyl and R⁴ is hydrogen, alkyl, alkoxy, or hydroxyl-substituted alkoxy, (b) a mixture of an azetidinium polymer and an acidic salt of a guanidine polymer comprised of monomer units having the structural formula (IV) as defined above, and (c) a copolymer of an azetidinium monomer and a guanidine monomer, (2) up to 40 wt. % of an optional film-forming binder, and (3) a liquid vehicle, wherein the sizing agent is admixed with the liquid vehicle prior to direct application of the sizing composition to the substrate surface, and (B) applying to the sized paper substrate a dye composition containing a reactive dye having ionizable and/or nucleophilic groups capable of reacting with the sizing agent thereby providing a sized substrate, wherein if the sizing agent is (a) or (c), then film-forming binder is present and the sizing agent represents approximately 5 wt. % to 95 wt. % of the sizing composition, based upon total solids weights of the sizing composition after drying.
 6. The paper product of claim 2, wherein the guanidine polymer is a homopolymer.
 7. The paper product of claim 2, wherein the guanidine polymer is a copolymer.
 8. The paper product of claim 2, wherein R³ and R⁴ are hydrogen.
 9. The paper product of claim 3, wherein the azetidinium polymer is comprised of monomer units having the structural formula

in which: R¹ and R² are independently lower alkylene, X⁻ is an anionic, organic or inorganic counterion, and Y¹, Y² and Y³ are selected from the group consisting of hydrogen, hydroxyl, halo, alkoxy, alkyl, amino, carboxy, acetoxy, cyano and sulfhydryl.
 10. The paper product of claim 9, wherein: R¹ and R² are methylene, X⁻ is selected from the group consisting of halide, acetate, methane sulfonate, succinate, citrate, malonate, fumarate, oxalate and hydrogen sulfate, Y¹ and Y³ are independently hydrogen or lower alkyl, and Y² is hydrogen or hydroxyl.
 11. The paper product of claim 10, wherein, in the azetidinium polymer, Y¹ and Y³ are hydrogen and Y² is hydroxyl.
 12. The paper product of claim 3, wherein R³ and R⁴ are hydrogen.
 13. The paper product of claim 9, wherein R³ and R⁴ are hydrogen.
 14. The paper product of claim 10, wherein R³ and R⁴ are hydrogen.
 15. The paper product of claim 4, wherein the azetidinium monomer unit has the structural formula

in which: R¹ and R² are independently lower alkylene, X⁻ is an anionic, organic or inorganic counterion, and Y¹, Y² and Y³ are selected from the group consisting of hydrogen, hydroxyl, halo, alkoxy, alkyl, amino, carboxy, acetoxy, cyano and sulfhydryl, and the guanidine monomer unit has the structural formula

wherein n is an integer in the range of 1 to 10 inclusive, R³ is hydrogen or lower alkyl and R⁴ is hydrogen, alkyl, alkoxy, or hydroxyl-substituted alkoxy.
 16. The paper product of claim 15, wherein: R¹ and R² are methylene, X⁻ is selected from the group consisting of halide, acetate, methane sulfonate, succinate, citrate, malonate, fumarate, oxalate and hydrogen sulfate, Y¹ and Y³ are independently hydrogen or lower alkyl, and Y² is hydrogen or hydroxyl.
 17. The paper product of claim 1, wherein the liquid vehicle is aqueous.
 18. The paper product of claim 1, wherein the film-forming binder is present in the sizing composition.
 19. The paper product of claim 18, wherein the film-forming binder represents approximately 1 wt. % to 25 wt. % of the sizing composition composition, based upon total solids weight of the composition after drying.
 20. The paper product of claim 18, wherein the film-forming binder is selected from the group consisting of polysaccharides, polypeptides, synthetic vinyl polymers, cationic film-forming binders, and derivatives thereof.
 21. The paper product of claim 20, wherein the film-forming binder is a polysaccharide or a derivative thereof.
 22. The paper product of claim 20, wherein the polysaccharide is starch.
 23. The paper product of claim 21, wherein the polysaccharide is a cellulosic polymer.
 24. The paper product of claim 21, wherein the polysaccharide is dextran.
 25. The paper product of claim 20, wherein the film-forming binder is a polypeptide.
 26. The paper product of claim 25, wherein the polypeptide is selected from the group consisting of collagen and gelatin.
 27. The paper product of claim 18, wherein the film-forming binder is a synthetic vinyl polymer.
 28. The paper product of claim 27, wherein the synthetic vinyl polymer is selected from the group consisting of poly(vinyl alcohol), poly(vinyl phosphate), poly(vinyl pyrrolidone), vinyl-pyrrolidone-vinyl acetate copolymers, vinyl alcohol-vinyl acetate copolymers, vinyl pyrrolidone-styrene copolymers, and poly(vinylamine).
 29. The paper product of claim 28, wherein the synthetic vinyl polymer is a vinyl pyrrolidone-styrene copolymer.
 30. The paper product of claim 28, wherein the film-forming binder is a cationic film-forming binder.
 31. The paper product of claim 30, wherein the cationic film-forming binder is selected from the group consisting of quaternized vinyl pyrrolidone-dimethylaminoethyl-methacrylate copolymer, dimethylaminoethyl-methacrylate-co-methyl methacrylate, polydiallyldimethyl ammonium chloride and quaternized aminoacrylate polymers. 